Process for preparing 3,3,3-trifluoroprop-1-ene

ABSTRACT

The present application provides a process of preparing 3,3,3-trifluoroprop-1-ene, comprising reacting 3-chloro-1,1,1-trifluoropropane with a base in an aqueous solvent component in the absence of a phase transfer catalyst.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application Ser.No. 62/469,668, filed Mar. 10, 2017, the disclosure of which isincorporated herein by reference in its entirety.

TECHNICAL FIELD

The application relates to the preparation of 3,3,3-trifluoroprop-1-enefrom 3-chloro-1,1,1-trifluoropropane in the presence of a base (e.g., anaqueous base) in an aqueous solvent component. The processes providedherein are conducted in the absence of a phase transfer catalyst.

BACKGROUND

Hydrofluoroolefins (HFOs), having low ozone depletion potential and lowglobal warming potentials, are regarded as candidates for replacingsaturated CFCs (chlorofluorocarbons) and HCFCs(hydrochlorofluorocarbons). HFOs can be employed in a wide range ofapplications, including their use as refrigerants, solvents, foamexpansion agents, cleaning agents, aerosol propellants, dielectrics,fire extinguishants, and power cycle working fluids.

SUMMARY

The present disclosure provides a dehydrohalogenation process in theabsence of organic solvents and dehydrohalogenation catalysts, includingphase transfer catalysts. Accordingly, the present application providesa process of preparing 3,3,3-trifluoroprop-1-ene, comprising reacting3-chloro-1,1,1-trifluoropropane with a base in an aqueous solventcomponent, wherein the reacting is conducted in the absence of a phasetransfer catalyst. In some embodiments, the aqueous solvent componentcomprises 0 to 40% w/w of an organic solvent. In some embodiments, theaqueous solvent component does not comprise an organic solvent (i.e.,the process is conducted in the absence of an organic solvent).

In another aspect, the present application further provides a process ofpreparing a mixture of 3,3,3-trifluoroprop-1-ene (HFO-1243zf) and2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), comprising reacting amixture of 3-chloro-1,1,1-trifluoropropane (HCFC-253fb) and1,1,1-trifluoro-2,3-dichloropropane (HCFC-243db) with a base in anaqueous solvent component, wherein the reacting is conducted in theabsence of a phase transfer catalyst. In some embodiments, the aqueoussolvent component comprises 0 to 40% of an organic solvent. In someembodiments, the aqueous solvent component does not comprise an organicsolvent (i.e., the process is conducted in the absence of an organicsolvent).

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although methods and materialssimilar or equivalent to those described herein can be used in thepractice or testing of embodiments of the present invention, suitablemethods and materials are described below. All publications, patentapplications, patents, and other references mentioned herein areincorporated by reference in their entirety, unless a particular passageis cited. In case of conflict, the present specification, includingdefinitions, will control. In addition, the materials, methods, andexamples are illustrative only and not intended to be limiting.

DETAILED DESCRIPTION

Heretofore, phase transfer catalysts (PTCs) have been used to prepareHFOs. Although the PTCs accelerate the reactions, they also pose anenvironmental problem, as it is necessary to dispose of these spentcatalysts. Further, the use of phase transfer catalysts increases thecosts of dehydrohalogenation reactions, as well as adding complexity andcost to the work-up steps of the process as the catalyst needs to beseparated from the organic and aqueous phases.

Eliminating the use of phase transfer catalysts and organic solventcomponents reduces the costs of these dehydrohalogenation reactionssince they can be expensive. In addition, their elimination would makewaste disposal easier and less expensive. Further, the elimination ofphase transfer catalysts would simplify dehydrohalogenation reactions byreducing the need of recycling and recovering the catalysts from theprocess. Finally, because catalysts lower the activation energy of thedehydrohalogenation reactions, there is more of a tendency for thedehydrochlorinated product to break down and waste the startingmaterial. Elimination of the phase transfer catalysts in thedehydrohalogenation reaction would reduce this risk. Thus, there is aneed to conduct dehydrohalogenation reactions in the absence of phasetransfer catalysts and organic solvent components in order to reducecosts and complexity of the process.

The foregoing general description and the following detailed descriptionare exemplary and explanatory only and are not restrictive of theinvention, as defined in the appended claims. Other features andbenefits of any one or more of the embodiments will be apparent from thefollowing detailed description, and from the claims.

Definitions and Abbreviations

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a process,method, article, or apparatus that comprises a list of elements is notnecessarily limited to only those elements but may include otherelements not expressly listed or inherent to such process, method,article, or apparatus. Further, unless expressly stated to the contrary,“or” refers to an inclusive or and not to an exclusive or. For example,a condition A or B is satisfied by any one of the following: A is true(or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

Also, use of “a” or “an” are employed to describe elements andcomponents described herein. This is done merely for convenience and togive a general sense of the scope of the invention. This descriptionshould be read to include one or at least one and the singular alsoincludes the plural unless it is obvious that it is meant otherwise.

When an amount, concentration, or other value or parameter is given aseither a range, preferred range or a list of upper preferable valuesand/or lower preferable values, this is to be understood as specificallydisclosing all ranges formed from any pair of any upper range limit orpreferred value and any lower range limit or preferred value, regardlessof whether ranges are separately disclosed. Where a range of numericalvalues is recited herein, unless otherwise stated, the range is intendedto include the endpoints thereof, and all integers and fractions withinthe range.

As used herein, the term “consisting essentially of” is used to define acomposition, method that includes materials, steps, features,components, or elements, in addition to those literally disclosedprovided that these additional included materials, steps, features,components, or elements do not materially affect the basic and novelcharacteristic(s) of the claimed invention, especially the mode ofaction to achieve the desired result of any of the processes of thepresent invention. The term “consists essentially of” or “consistingessentially of” occupies a middle ground between “comprising” and“consisting of”.

The term “alkyl”, as used herein, either alone or in combinationincludes cyclic or acyclic and straight-chain or branched alkyl groups,such as, methyl, ethyl, n-propyl, i-propyl, or the different isomersthereof. For example, the alkyl group may contain 1-10 carbon atoms. Thealkyl group may be a lower alkyl which contains from 1 to 6 carbonatoms.

“Aryl”, as defined herein, whether used alone or in combination, refersto an aromatic ring containing 6, 10, 14, or 18 ring carbon atoms.Examples include phenyl, α-naphthyl, β-naphthyl, anthracenyl and thelike.

By the use of the term “arylalkyl”, it is meant that the alkyl group, asdefined herein, is attached to the main chain at one end and aryl groupon the other end. Examples include benzyl, phenethyl, phenpropyl and thelike.

The term “heterocyclic”, when used alone or in combination, refers to anaromatic, partially aromatic, partially saturated or saturatedmonocyclic, bicyclic or tricyclic ring system containing 3 to 14 ringatoms, in which 1, 2, or 3 of the ring atoms are independently selectedfrom nitrogen, oxygen and sulfur and the remaining ring atoms are carbonatoms. The heterocyclic ring may be completely heteroaromatic or partlyheteroaromatic, in which one of the rings fused to the heterocyclic ringis aromatic. Thus, heterocyclic, as used herein, includesheteroaromatic. In addition, the heterocyclic ring may contain one ormore double bonds, either between two carbons, between two nitrogenatoms or between a nitrogen atom and a carbon atom. The designation ofthe aza, oxa or thio as a prefix before heterocyclyl define that atleast a nitrogen, oxygen or sulfur atom is present, respectively, as aring atom. The nitrogen atom of a heterocyclic compound may be a basicnitrogen atom. The nitrogen or sulfur atom of the heterocyclic compoundmay also be optionally oxidized to the corresponding N-oxide, S-oxide orS,S-dioxide. When a heteroaryl is substituted by a hydroxy group, italso includes its corresponding tautomer. Exemplary heterocyclicincludes piperidyl, pyrrolidinyl, piperazinyl, morpholinyl,tetrahydrofuryl, thiomorpholinyl, thiazolidinyl, 1,3-dioxolanyl,1,4-dioxanyl, tetrahydrothiophenyl, tetrahydrothiopyranyl. pyrazinyl,thienyl, isothiazolyl, oxazolyl, pyrazolyl, furanyl, pyrrolyl,1,2,4-thiadiazolyl, pyridazinyl, quinoxalinyl, phthalazinyl,imidazo[1,2-a]pyridine, imidazo[2,1-b]thiazolyl, benzofuranyl,azaindolyl, benzimidazolyl, benzothienyl, thienopyridyl,thienopyrimidyl, pyrrolopyridyl, imidazopyridyl, benzoazaindolyl,1,2,4-triazinyl, benzothiazolyl, imidazolyl, indolyl, indolizinyl,isoxazolyl, isoquinolinyl, isothiazolyl, oxadiazolyl, pyrazinyl,pyridazinyl, pyrazolyl, pyridyl, pyrimidinyl, pyrrolyl, quinazolinyl,quinolinyl, 1,3,4-thiadiazolyl, thiazolyl, thienyl, and triazolyl andthe like.

The term “halogen” refers to fluoro, chloro, bromo and iodo.

The term “dehydrohalogenation”, as used herein, means a process duringwhich hydrogen and halogen, e.g. Cl, Br or I on adjacent carbons in amolecule are removed to form the corresponding olefin.

As used herein, the term “dehydrochlorination” refers to a processduring which hydrogen and chlorine on adjacent carbons in a molecule areremoved to form the corresponding olefin.

The term “aqueous solvent” refers to a solvent comprised of water or amixture of one or more solvents mixed with water. In some embodiments,water is the sole solvent. However, the aqueous solvent may alsocomprise water mixed with a polar solvent, such as methanol, ethanol1-propanol, 2-propanol, 1, 3-butandiol, 1,2-butanediol, acetonitrile,acetaldehyde, acetone, ethylene glycol, propylene glycol,tetrahydrofuran, triethylene glycol, 1,3-propanediol, glycerol, 1,4dioxane, and the like.

The term “mixing”, as defined herein, refers to the process of stirringthe reactants (e.g., 3-chloro-1,1,1-trifluoropropane and base), at aparticular mixing power of, for example, about 0.1 to about 50horsepower per 1000 gallons of the reaction mixture (e.g., an aqueousreaction mixture). The stirring (i.e., mixing) can be effected, forexample, by mechanical means (e.g., a stirrer or in a shaker so that thereactants are substantially thoroughly mixed with one another underconditions sufficient to dehydrohalogenate the3-chloro-1,1,1-trifluoropropane to produce 3,3,3-trifluoroprop-1-ene)and by other means known in the art or as described herein.

Accordingly, in some embodiments, mixing is provided by a mechanicalagitator. However the mixing power input can alternatively be providedby other methods. These methods are known in the industry and includeusing the mixing provided by gas bubbles from gas added to the vessel orgenerated within the vessel by vaporization of liquid. Mixing can alsobe provided by withdrawing the liquid from the vessel to a pump andpumping the liquid back into the vessel. A static mixer, rotor statorheads, or other device intended to mix the contents can be present inthe circulation path of the liquid to provide additional mixing powerinput. Mixing can be provided by a single method or by a combination oftwo or more methods.

In some embodiments, the reactor stirs the reaction mixture (e.g.,3-chloro-1,1,1-trifluoropropane and base, and amine if present) byimparting to the agitator the power to stir the liquid in the tank. Thepower input is calculated based on the combination of severalparameters, including the geometry of the vessel, design of baffles, ifany, design of the impeller, and speed at which the impeller rotates.This calculation is performed by one of ordinary skill in the art. Inthe process described herein, to maximize the yield, in an embodimentthe base are mixed together, generating small bubbles and highinterphase surface area. Autoclave reactors are examples of reactorsthat could achieve the above-identified horsepower per gallon of liquid.In an embodiment, about 0.1 to about 50 horsepower/1000 gallon of liquidis imparted to the agitator, making the agitator agitate the reactionmixture, while in another embodiment, about 0.5 to about 40horsepower/1000 gallon of liquid is imparted to the agitator, making theagitator agitate the reaction mixture, and another embodiment, about 1to about 35 horsepower/1000 gallon of liquid is imparted to theagitator, causing the agitator to agitate the reaction mixture.

As used herein, “caustic” refers to a base that would dissociate whenplaced in water. Examples include an alkali metal oxides, hydroxide, oramide, such as sodium or potassium oxide or sodium or potassiumhydroxide or sodium or potassium amide; or alkaline earth metalhydroxide, alkaline earth metal oxide or amide, alkali metal carbonateor alkali metal phosphate or alkali metal carboxylate.

The process of the present reaction, in an embodiment, is carried out inthe presence of a base that would dissociate when placed in water.Examples include metal oxides, hydroxides, amides, carbonates,phosphates or carboxylates. However, as defined the term “base” excludesamines, including ammonia. Unless indicated to the contrary, the term“amine” includes ammonia.

As used herein, “metal” in the terms-metal hydroxide base, metalcarbonate base, a metal phosphate base, or a metal fluoride base-refersto an alkali metal or alkaline earth metal.

As used herein, by the term “alkali metal hydroxide”, refers to acompound or mixture of compounds selected from the group consisting oflithium hydroxide, sodium hydroxide, potassium hydroxide, rubidiumhydroxide and cesium hydroxide. In some embodiments, the alkali metalhydroxide is sodium hydroxide.

As used herein, the term “alkali metal amide”, refers to a compound ormixture of compounds selected from the group consisting of lithiumamide, sodium amide, potassium amide, rubidium amide, and cesium amide.

As used herein, the term “alkaline earth metal hydroxide”, refers to acompound or mixture of compounds selected from the group consisting ofberyllium hydroxide, magnesium hydroxide, calcium hydroxide, strontiumhydroxide, and barium hydroxide.

As used herein, the term “alkaline earth metal amide” refers to acompound or mixture of compounds selected from the group consisting ofberyllium amide, magnesium amide, calcium amide, strontium amide, andbarium amide.

As used herein, the term “alkali metal carbonate”, refers to a compoundor mixture of compounds selected from the group consisting of lithiumcarbonate, sodium carbonate, potassium carbonate, rubidium carbonate,and cesium carbonate.

As used herein, the term “alkaline earth metal carbonate” refers to acompound or mixture of compounds selected from the group consisting ofberyllium carbonate, magnesium carbonate, calcium carbonate, strontiumcarbonate, and barium carbonate.

As used herein, the term “alkali metal oxide”, refers to a compound ormixture of compounds selected from the group consisting of lithiumoxide, sodium oxide, potassium oxide, rubidium oxide, and cesium oxide.

As used herein, the term “alkaline earth metal oxide” refers to acompound or mixture of compounds selected from the group consisting ofberyllium oxide, magnesium oxide, calcium oxide, strontium oxide, andbarium oxide.

As used herein, the term “alkali metal phosphate”, refers to a compoundor mixture of compounds selected from the group consisting of lithiumphosphate, sodium phosphate, potassium phosphate, rubidium phosphate,and cesium phosphate.

As used herein, the term “alkaline earth metal phosphate” refers to acompound or mixture of compounds selected from the group consisting ofberyllium phosphate, magnesium phosphate, calcium phosphate, strontiumphosphate, and barium phosphate.

In an embodiment, an amine or ammonia is additionally present. Thedehydrohalogenation reaction, in an embodiment, is conducted in thepresence of the base described hereinabove and an amine of the formulaR1R2R3N, wherein R1, R2, and R3 are as defined hereinabove. The alkylgroup, heterocyclic group, aryl group, aralkyl group, and theheterocyclicalkyl group of R1, R2 and R3 can be substituted orunsubstituted. Substituted alkyl group, substituted heterocyclic group,substituted aryl group, substituted aralkyl group or substitutedheterocyclicalkyl herein means that one or more hydrogens on carbonatoms have been substituted by functional groups, such as hydroxylgroups, alkoxy groups, halogens, amino groups, and the like. The amine,as defined herein, can be aliphatic amine, aromatic amine, orheterocyclic amine or mixtures thereof. In some embodiments, the amineis an aliphatic amine.

In some embodiments, when present, the amine can be primary amine,secondary amine, tertiary amine, or mixtures thereof. In someembodiments, the amine is a primary unsubstituted alkyl amine of theformula RNH₂ wherein R is a C₁-C₁₆ unsubstituted alkyl group. In someembodiments, the amine is primary unsubstituted alkyl amine of theformula R1NH₂ wherein R1 is a C₁-C₃ unsubstituted alkyl group. Examplesof primary unsubstituted alkyl amines include methylamine, ethylamine,propylamine, isopropylamine, butylamine, sec-butylamine,tert-butylamine, amylamine, isoamylamine, tert-amylamine, hexylamine,and mixtures thereof.

In some embodiments, when present, the amine is secondary unsubstitutedalkyl amine of the formula R1R2NH wherein each R1 and R2 isindependently a C₁-C₆ unsubstituted alkyl group. In some embodiments,the amine is secondary unsubstituted alkyl amine of the formula R1R2NHwherein each R is independently a C₁-C₃ unsubstituted alkyl group.Examples of secondary unsubstituted alkyl amines include dimethylamine,diethylamine, dipropylamine, diisopropylamine, dibutylamine,di-sec-butylamine, diamylamine, dihexylamine, and mixtures thereof.

In some embodiments, the amine is tertiary unsubstituted alkyl amine ofthe formula R1R2R3N wherein each R1, R2 and R3 is independently a C₁-C₆unsubstituted alkyl group. In some embodiments, when present, the amineis tertiary unsubstituted alkyl amine of the formula R1R2R3N whereineach R1, R2 and R3 is independently a C₁-C₃ unsubstituted alkyl group.Examples of tertiary unsubstituted alkyl amines include trimethylamine,triethylamine, tripropylamine, tributylamine, triamylamine,trihexylamine, N,N-dimethylethylamine, N,N-dimethylpropylamine,N,N-dimethylbutylamine, and mixtures thereof.

In other embodiments, when present, the amine is selected from the groupconsisting of methylamine, dimethylamine, trimethylamine, ethylamine,diethylamine, triethylamine, propylamine, isopropylamine, dipropylamine,diisopropylamine, tripropylamine, butylamine, sec-butylamine,tert-butylamine, dibutylamine, tributylamine, di-sec-butylamine,amylamine, isoamylamine, tert-amylamine, diamylamine, triamylamine,hexylamine, dihexylamine, trihexylamine, 1,1,3,3-tetramethylbutylamine),N,N-dimethylethylamine, N,N-dimethylpropylamine, N,N-dimethylbutylamine,and mixtures thereof.

In other embodiments, the amine has one or two or three substitutedalkyl groups thereon, which may be the same or different wherein one ormore hydrogens on carbon atoms have been substituted by hydroxyl groups.Examples of such amine include ethanolamine (H₂NCH₂CH₂OH),diethanolamine, triethanolamine, tris(hydroxymethyl)aminomethane((HOCH₂)₃CNH₂), 2-(methylamino)ethanol (CH₃NHCH₂CH₂OH),2-(ethylamino)ethanol (CH₃CH₂NHCH₂CH₂OH), 2-(propylamino)ethanol(CH₃CH₂CH₂NHCH₂CH₂OH), 2-(isopropylamino)ethanol ((CH₃)₂CHNHCH₂CH₂OH),2-(butylamino)ethanol (CH₃(CH₂)₃NHCH₂CH₂OH), 2-(tert-butylamino)ethanol((CH₃)₃CNHCH₂CH₂OH), triisopropanolamine ([CH₃CH(OH)CH₂]₃N),N,N-dimethylethanolamine (HOCH₂CH₂N(CH₃)₂), 1-dimethylamino-2-propanol((CH₃)₂NCH₂CH(OH)CH₃), 3-dimethylamino-1-propanol ((CH₃)₂N(CH₂)₃OH),2-amino-2-methyl-1-propanol ((CH₃)₂C(NH₂)CH₂OH), and mixtures thereof.

In still other embodiments, one of R1, R2 and R3 of the amine has aC₁-C₆ substituted alkyl group thereon wherein one or more hydrogens oncarbon atoms have been substituted by hydroxyl groups, and the remaininggroups are independently selected from the group consisting of hydrogenand C₁-C₁₆ unsubstituted alkyl groups. Examples of such amine includeethanolamine (H₂NCH₂CH₂OH), tris(hydroxymethyl)aminomethane((HOCH₂)₃CNH₂), 2-(methylamino)ethanol (CH₃NHCH₂CH₂OH),2-(ethylamino)ethanol (CH₃CH₂NHCH₂CH₂OH), 2-(propylamino)ethanol(CH₃CH₂CH₂NHCH₂CH₂OH), 2-(isopropylamino)ethanol ((CH₃)₂CHNHCH₂CH₂OH),2-(butylamino)ethanol (CH₃(CH₂)₃NHCH₂CH₂OH), 2-(tert-butylamino)ethanol((CH₃)₃CNHCH₂CH₂OH), N,N-dimethylethanolamine (HOCH₂CH₂N(CH₃)₂),1-dimethylamino-2-propanol ((CH₃)₂NCH₂CH(OH)CH₃),3-dimethylamino-1-propanol ((CH₃)₂N(CH₂)₃OH),2-amino-2-methyl-1-propanol ((CH₃)₂C(NH₂)CH₂OH), and mixtures thereof.In some embodiments, at least one R1, R2 and R3 group of the amine is aC₁-C₆ substituted alkyl group wherein one or more hydrogens on carbonatoms have been substituted by amino groups, and the rest of the groups,are independently selected from the group consisting of hydrogen andC₁-C₁₆ unsubstituted alkyl groups. Examples of such amines include3-(dimethylamino)propylamine ((CH₃)₂N(CH₂)₃NH₂),3-(diethylamino)propylamine ((C₂H₅)₂N(CH₂)₃NH₂), and mixtures thereof.

In some embodiments, when present, the amine is polyamine. Examples ofpolyamines include ethylene diamine, 1,2-propylenediamine,1,3-propylenediamine, 1,4-diaminobutane, 1,3-diaminopentane,1,5-diaminopentane, 1,6-diaminohexane, 2-methyl-1,5-pentanediamine,spermidine (N-(3-aminopropyl)butane-1,4-diamine), spermine(N,N′-bis(3-aminopropyl)butane-1,4-diamine), diethylenetriamine,triethylenetetramine, and mixtures thereof.

In some embodiments, the amine, when present is heterocyclic amine.Examples of heterocyclic amines include pyrrolidine, pyrroline(including 1-pyrroline, 2-pyrroline and 3-pyrroline), piperidine,piperazine, morpholine, imidazole, pyrazole, pyridine, pyrimidine,pyridazine, pyrazine, pyridine, bipyridine (including 2,2′-bipyridine,4,4′-bipyridine, 2,3′-bipyridine, and 3,4′-bipyridine, etc.), andmixtures thereof.

In other embodiments, the amine, when present, is hydrazine (NH₂NH₂),hydrazine derivatives, such as alkyl hydrazines or arylhydrazines oraralkyl hydrazines and the like and mixtures thereof. Examples ofhydrazine derivatives include methylhydrazine (CH₃NHNH₂),1,1-dimethylhydrazine ((CH₃)₂NNH₂), 1,2-dimethylhydrazine (CH₃NHNHCH₃),phenylhydrazine, 2,4-dinitrophenylhydrazine, and mixtures thereof.

In some embodiments, the amine, when present, is an aromatic amine.Examples of aromatic amines include aniline, o-toluidine, m-toluidine,p-toluidine, xylidine, 2,4,6-trimethylaniline, o-anisidine, m-anisidine,p-anisidine, N-methylaniline, N,N-dimethylaniline, N-ethylaniline,N,N-diethylaniline, and mixtures thereof.

In an embodiment, mixtures of any of the aforementioned amines may alsobe used in this disclosure.

In some embodiments, the amine, when present, is selected from the groupconsisting of heterocyclic amines, hydrazine and its derivatives, andmixtures thereof. In some embodiments, the amine is a heterocyclicamine, and mixtures thereof.

In an embodiment, one of R1, R2 and R3 is hydrogen and the other of R1,R2 and R3 are independently lower alkyls. In an embodiment, R2 and R3may be the same or different. In another embodiment, R1, R2 and R3 arethe same or different and other than hydrogen. For example, R1, and R2and R3 are independently lower alkyls. In still another embodiment, R1is phenyl, alkyl, pyridine, alkyl substituted pyridine and R2 and R3 areas defined hereinabove. In another embodiment, the amine is hydrazine.

In an embodiment, the amine, when present, is trialkyl or dialkyl amineand preferred amines are trialkylamine.

It should be noted that all combinations and permutations of R1, R2, andR3 are contemplated.

In an embodiment, the mole ratio of amine, when present, tohalofluoroalkane ranges from about 0.02 to about 3. In one embodiment,the mole ratio ranges from about 0.05 to about 0.5, and in anotherembodiment, the mole ratio ranges from about 0.05 to about 0.25.

In addition, in an embodiment, the mole ratio of amine, when present, tobase ranges from about 0.05 to about 3, and in another embodiment, fromabout 0.05 to about 1, and in a still further embodiment, from about0.05 to about 0.5.

As described herein, the processes of the present application areconducted in the absence of a catalyst. As used herein, the term“catalyst”, refers to a substance that speeds up the chemical reaction,but is not consumed by the reaction; thus it can be recovered chemicallyunchanged at the end of the reaction. A phase transfer catalyst is aheterogenous catalyst that facilitates the migration of a reactant fromone phase into another phase where the reaction occurs. For example, aphase transfer catalyst is a catalyst which facilitates the transfer ofan ionic compound into an organic phase from, for example, a waterphase. If water is used as a solvent, an aqueous or inorganic phase ispresent as a consequence of the base (e.g., alkali metal hydroxide) andan organic phase is present as a result of the (chloro)fluorocarbon. Thephase transfer catalyst facilitates the reaction of these dissimilarcomponents. While various phase transfer catalysts may function indifferent ways, their mechanism of action is not determinative of theirutility in the present invention provided that they facilitate thedehydrohalogenation reaction. For example, the processes provided hereinmay be conducted in the absence of a phase transfer catalyst which isionic or neutral. In some embodiments, the processes provided herein areconducted in the absence of a phase transfer catalyst selected from thegroup consisting of crown ethers, onium salts, cryptands, andpolyalkylene glycols and derivatives thereof (e.g., fluorinatedderivatives thereof). In some embodiments, process provided herein isconducted in the absence of a phase transfer catalyst provided inInternational Patent Application No. PCT/US2016/050918, the disclosureof which is incorporated herein by reference in its entirety.

Derivatives of the above crown ethers are considered phase transfercatalysts such as dibenzyl-18-crown-6, dicyclohexanyl-18-crown-6,dibenzyl-24-crown-8 and dibenzyl-12-crown-4, are also excluded. Othercompounds analogous to the crown ethers which differ by the replacementof one or more of the oxygen atoms by other kinds of donor atoms,particularly N or S are also excluded. In addition, fluorinatedderivatives, such as compounds in which one or more of the hydrogenatoms are substituted by fluorine, are excluded as well.

Cryptands are another class of compounds that are excluded. These arethree dimensional polymacrocyclic chelating agents that are formed byjoining bridgehead structures with chains that contain properly spaceddonor atoms. The donor atoms of the bridges may all be O, N, or S, orthe compounds may be mixed donor macrocycles in which the bridge strandscontain combinations of such donor atoms. For example, cryptands whichinclude bicyclic molecules that result from joining nitrogen bridgeheadswith chains of (—OCH₂CH₂—) groups, for example as in [2.2.2]cryptand(4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane, availableunder the brand names Kryptand 222 and Kryptofix 222), are excluded.

Onium salts of any kind, including quaternary phosphonium salts andquaternary ammonium salts, useful as catalysts, are excluded. Specificexamples of such phosphonium salts and quaternary ammonium salts whichare excluded include tetramethylammonium chloride, tetramethylammoniumbromide, benzyltriethylammonium chloride, methyltrioctylammoniumchloride (available commercially under the brands Aliquat 336 and Adogen464), tetra-n-butylammonium chloride, tetra-n-butylammonium bromide,tetra-n-butylammonium hydrogen sulphate, tetra-n-butylphosphoniumchloride, tetraphenylphosphonium bromide, tetraphenylphosphoniumchloride, triphenylmethylphosphonium bromide andtriphenylmethylphosphonium chloride and benzyltriethylammonium chlorideare excluded.

Other onium salts which exhibit high temperature stabilities (e.g. up toabout 200° C.), for example, 4-dialkylaminopyridinium salts,tetraphenylarsonium chloride, bis [tris (dimethylamino) phosphine]iminium chloride and tetrakis [tris (dimethylamino) phosphinimino]phosphonium chloride are also excluded.

Polyalkylene glycol compounds useful as phase transfer catalysts arealso excluded. For example, polyalkylene glycol compounds represented bythe formula R⁶O(R⁵O)_(m)R⁷ wherein R⁵ is a C₁₋₁₀ alkylene group, each ofR⁶ and R⁷ are, independently H, C₁₋₁₀ alkyl group, an aryl group, (i.e.,an aromatic group containing 6, 10 or 14 ring carbon atoms or heteroarylgroup containing 5 to 14 ring atoms and 1 to 3 heteroatoms selected fromN, O and S and the remainder ring atoms are carbon atoms, e.g., phenyl,naphthyl or pyridinyl) or an arylalkyl group (e.g. benzyl or C₁₋₁₀alkyl-substituted phenyl), and m is an integer of at least 2 are alsoexcluded. Such polyalkylene glycols such as diethylene glycol,triethylene glycol, tetraethylene glycol, pentaethylene glycol,hexaethylene glycol, diisopropylene glycol, dipropylene glycol,tripropylene glycol, tetrapropylene glycol and tetramethylene glycol,monoalkyl glycol ethers such as monomethyl, monoethyl, monopropyl andmonobutyl ethers of such glycols, dialkyl ethers such as tetraethyleneglycol dimethyl ether and pentaethylene glycol dimethyl ether, phenylethers, benzyl ethers of such glycols, and polyalkylene glycols such aspolyethylene glycol (average molecular weight about 300) andpolyethylene glycol (average molecular weight about 400) and the dialkyl(e.g. dimethyl, dipropyl, dibutyl)ethers of such polyalkylene glycolsare excluded.

The following abbreviations may be used throughout the presentapplication:

CFC: chlorofluorocarbon

HFO: hydrofluoroolefin

HCFC: hydrochlorofluorocarbon

HFO-1243zf (i.e., 1243zf): 3,3,3-trifluoroprop-1-ene

HFO-1234yf (i.e., 1234yf): 2,3,3,3-tetrafluoroprop-1-ene

HCFC-243db: 1,1,1-trifluoro-2,3-dichloropropane

HCFC-244bb: 2-chloro-1,1,1,2-tetrafluoropropane

HCFC-253fb (i.e., 253fb): 3-chloro-1,1,1-trifluoropropane

HCFO-1233xf (i.e., 1233xf): 2-chloro-3,3,3-trifluoroprop-1-ene

HFC-254fb: (i.e., 254fb): 1,1,1,3-tetrafluoropropane

HFC-245cb: 1,1,1,2,2-pentafluoropropane

PTC: phase transfer catalyst

psig: pounds per square inch gauge

RPM: revolutions per minute

Process of Preparing 3,3,3-Trifluoroprop-1-ene

Accordingly, the present application provides a process of preparing3,3,3-trifluoroprop-1-ene (i.e., “HFO-1243zf” or “1243zf”) comprisingreacting 3-chloro-1,1,1-trifluoropropane (i.e., “HCFC-253fb” or “253fb”)with a base, wherein the reacting is conducted in the absence of a phasetransfer catalyst. A schematic representation of the process providedherein is shown below in Scheme 1.

Because phase transfer catalysts (e.g., dehydrohalogenation catalystssuch as dehydrochlorination catalysts) are not used in the processesdescribed herein, the costs of the reactions are minimized, as thesecatalysts can be expensive. These catalysts need to be separated fromthe product and are difficult to dispose, which adds additional expenseto a catalyzed system. The process provided herein, which is conductedin the absence of catalysts, does not have this added expense. Further,the elimination of phase transfer catalysts simplifies thedehydrohalogenation reaction by reducing the need of recycling andrecovering these catalysts from the process. Finally, since thecatalysts lower the activation energy of the dehydrohalogenationreactions, and since there is more of a tendency for thedehydrohalogenated product to break down and waste the startingmaterial, elimination of the phase transfer catalysts in thedehydrohalogenation reaction reduces this risk.

In some embodiments, the reacting is conducted in the absence of a phasetransfer catalyst. In some embodiments, the reacting is conducted in anaqueous solvent component. In some embodiments, the reacting isconducted in an aqueous solvent component and in the absence of a phasetransfer catalyst. In some embodiments, the reacting is conducted inwater and in the absence of a phase transfer catalyst.

In some embodiments, the reacting is conducted in the absence of a phasetransfer catalyst and the aqueous solvent component comprise 0 to 40%w/w of an organic solvent. In some embodiments, the reacting isconducted in the absence of a phase transfer catalyst and the aqueoussolvent component comprises 0 to 30% w/w of an organic solvent. In someembodiments, the reacting is conducted in the absence of a phasetransfer catalyst and the aqueous solvent component comprises 0 to 20%w/w of an organic solvent. In some embodiments, the reacting isconducted in the absence of a phase transfer catalyst and the aqueoussolvent component comprises 0 to 10% w/w of an organic solvent. In someembodiments, the reacting is conducted in the absence of a phasetransfer catalyst and the aqueous solvent component does not comprise anorganic solvent. In some embodiments, the reacting is conducted in theabsence of a phase transfer catalyst and an organic solvent. In someembodiments, the reacting is conducted in the absence of a phasetransfer catalyst and an organic solvent component selected from analiphatic alcohol, such as methanol, ethanol, n-propanol, isopropanol,butanol, and the like.

In some embodiments, the reacting is conducted as a liquid phasereaction. In some embodiments, the reacting is performed in the presenceof water.

Exemplary bases useful in the processes provided herein include metalbases such as metal oxides (e.g., alkali metal oxides or alkaline earthmetal oxides), metal hydroxides (e.g., alkali metal hydroxides oralkaline earth metal hydroxides), metal amides (e.g., alkali metalamides or alkaline earth metal amides), metal carbonates (e.g. alkalimetal carbonates or alkaline earth metal carbonates), or metalphosphates (e.g., alkali metal phosphates or alkaline earth metalphosphates. In some embodiments, the metal base is a transition metalbase (e.g., zinc hydroxide). Exemplary metals included in the metalbases provided herein include, but are not limited to, sodium,potassium, lithium, cesium, calcium, zinc, and the like.

In some embodiments, the base is an alkali metal hydroxide.

In some embodiments, the base is mixed with water to form an aqueousbase (e.g., an aqueous basic suspension) or an aqueous basic solution.In some embodiments, the base is an aqueous base.

In some embodiments, the base is a metal hydroxide base, a metalcarbonate base, a metal phosphate base, or a metal fluoride base.

In some embodiments, the base is an alkali metal hydroxide base, analkaline earth metal hydroxide base, an alkali metal carbonate base, analkali metal phosphate base, or an alkali metal fluoride base.

In some embodiments, the base is an alkali metal hydroxide base.

In some embodiments, the base is NaOH, KOH, LiOH, CsOH, Ca(OH)₂,Zn(OH)₂, Na₂CO₃, K₂CO₃, K₃PO₄, Na₃PO₄, KF, or CsF.

Preferably, the base is KOH or NaOH.

In some embodiments, the base is NaOH.

In some embodiments, the base is KOH.

In some embodiments, the base is aqueous NaOH.

In some embodiments, the base is aqueous KOH.

In some embodiments, about 0.5 to about 10 molar equivalents of base isused based on one molar equivalent of 3-chloro-1,1,1-trifluoropropane.In some embodiments, about 1 to about 2 molar equivalents of base isused based on one molar equivalent of 3-chloro-1,1,1-trifluoropropane.In some embodiments, about 0.01 to about 5 molar equivalents of base isused based on one molar equivalent of 3-chloro-1,1,1-trifluoropropane.In some embodiments, about 0.02 to about 4 molar equivalents of base isused based on one molar equivalent of 3-chloro-1,1,1-trifluoropropane.In some embodiments, about 0.02 to about 2 molar equivalents of base isused based on one molar equivalent of 3-chloro-1,1,1-trifluoropropane.In some embodiments, about 0.05 to about 1.5 molar equivalents of baseis used based on one molar equivalent of3-chloro-1,1,1-trifluoropropane.

In some embodiments, the reacting is conducted at a temperature of fromabout 20° C. to about 100° C., for example, about 20° C. to about 100°C., about 20° C. to about 80° C., about 20° C. to about 60° C., about20° C. to about 40° C., about 20° C. to about 30° C., about 30° C. toabout 100° C., about 30° C. to about 80° C., about 30° C. to about 60°C., about 30° C. to about 40° C., about 40° C. to about 100° C., about40° C. to about 80° C., about 40° C. to about 60° C., about 60° C. toabout 100° C., about 60° C. to about 80° C., or about 80° C. to about100° C.

In some embodiments, the reacting is conducted at a temperature of fromabout 35° C. to about 80° C.

In some embodiments, the reacting is conducted at a temperature of fromabout 35° C. to about 65° C.

In some embodiments, the reacting is conducted at a temperature of fromabout 55° C. to about 65° C.

In some embodiments, the reacting is conducted at a temperature of fromabout 30° C. to about 40° C.

In some embodiments, the reacting is conducted at a pressure of about−10 psig to about 500 psig. In some embodiments, the reacting isconducted at a pressure of −10 psig to about 230 psig, for example, −10psig to about 230 psig, −10 psig to about 150 psig, −10 psig to about125 psig, −10 psig to about 100 psig, −10 psig to about 75 psig, −10psig to about 50 psig, −10 psig to about 25 psig, −10 psig to about 0psig, 0 psig to about 150 psig, 0 psig to about 125 psig, 0 psig toabout 100 psig, 0 psig to about 75 psig, 0 psig to about 50 psig, 0 psigto about 25 psig, 25 psig to about 150 psig, 25 psig to about 125 psig,25 psig to about 100 psig, 25 psig to about 75 psig, 25 psig to about 50psig, 50 psig to about 150 psig, 50 psig to about 125 psig, 50 psig toabout 100 psig, 50 psig to about 75 psig, 75 psig to about 150 psig, 75psig to about 125 psig, 75 psig to about 100 psig, 100 psig to about 150psig, 100 psig to about 125 psig, or 125 psig to about 150 psig.

In some embodiments, the reacting is conducted at a pressure of about 5psig to about 230 psig.

In some embodiments, the reacting is conducted at a pressure of about 5psig to about 150 psig.

In some embodiments, the reacting comprises mixing the3-chloro-1,1,1-trifluoropropane and base with a mixing power of fromabout 0.1 to about 50 horsepower per 1000 gallons of the reactionmixture, for example, about 0.1 to about 50, about 0.1 to about 40,about 0.1 to about 30, about 0.1 to about 20, about 0.1 to about 10,about 0.1 to about 1, about 1 to about 50, about 1 to about 40, about 1to about 30, about 1 to about 20, about 1 to about 10, about 10 to about50, about 10 to about 40, about 10 to about 30, about 10 to about 20,about 20 to about 50, about 20 to about 40, about 20 to about 30, about30 to about 50, about 30 to about 40, or about 40 to about 50 horsepowerper 1000 gallons of the reaction mixture.

In some embodiments, the reacting comprises stirring the3-chloro-1,1,1-trifluoropropane and base with a mixing power of fromabout 0.5 to about 40 horsepower per 1000 gallons of the reactionmixture.

In some embodiments, the reacting comprises stirring the3-chloro-1,1,1-trifluoropropane and base with a mixing power of fromabout 1 to about 35 horsepower per 1000 gallons of the reaction mixture.

In some embodiments, the reacting is conducted at a temperature of fromabout 35° C. to about 80° C. and at a pressure of about 5 psig to about230 psig.

In some embodiments, the reacting is conducted at a temperature of fromabout 55° C. to about 80° C. and at a pressure of about 5 psig to about230 psig.

In some embodiments, the reacting is conducted at a temperature of fromabout 35° C. to about 80° C. and at a pressure of about 5 psig to about150 psig.

In some embodiments, the reacting is conducted at a temperature of fromabout 30° C. to about 80° C. and at a pressure of about 5 psig to about150 psig.

The present application further provides a process of preparing3,3,3-trifluoroprop-1-ene, comprising reacting3-chloro-1,1,1-trifluoropropane with aqueous NaOH, wherein the reactingis performed at a temperature of from about 35° C. to about 80° C. andat a pressure of from about 5 psig to about 150 psig, and wherein thereacting is conducted in the absence of a phase transfer catalyst and anorganic solvent component.

In some embodiments, the reacting is conducted at a pressure of fromabout 5 psig to about 150 psig.

In some embodiments, the 3-chloro-1,1,1-trifluoropropane is prepared byreacting 1,1,1,3-tetrachloropropane with hydrofluoric acid. In someembodiments, the 3-chloro-1,1,1-trifluoropropane is produced as abyproduct, intermediate, or coproduct during a process of preparingHFO-1243zf.

In some embodiments, the 3-chloro-1,1,1-trifluoropropane is prepared byreacting 1,1,1-trifluoropropane with Cl₂.

The process described herein, in the presence or absence of an amine,may be conducted in the presence of an inert gas such as He, Ar, or N₂.In some embodiments, the inert gas is co-fed into the reactor with thestarting material.

In an embodiment, the process, described herein, in the presence orabsence of an amine, is conducted in the liquid phase an aqueous solventusing well-known chemical engineering practice, such as a continuousprocess, batch process, semi-continuous process or a combinationthereof.

Under the conditions described, and in all cases of a continuous, batch,or semi-continuous operation, the reaction is completed a relativelyshort time after initiated. In an embodiment, a reaction time up toabout 4 hours is sufficient. For example, in an embodiment, the reactiontime ranges from about 1 to about 120 minutes, while in anotherembodiment, the reaction time ranges from about 3 to about 60 minutesand in another embodiment, from about 5 to about 30 minutes.

The 3,3,3-trifluoroprop-1-ene is isolated using separation techniquesknown in the art, such as distillation, chromatography, extraction andthe like. In some embodiments, the 3,3,3-trifluoroprop-1-ene can beisolated by distillation directly from the reaction vessel.

The 3,3,3-trifluoroprop-1-ene can be used to prepare further compounds,including HFO-1234yf, which is useful for a variety of applications.Accordingly, in some embodiments, the process of further comprisesreacting the 3,3,3-trifluoroprop-1-ene with chlorine to make2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db), followed bydehydrochlorination to form 2-chlorine-3,3,3-trifluoropropene(HCFO-1233xf), followed by reaction with HF to form2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), and finallydehydrochlorination to form 2,3,3,3-tetrafluoropropene (HFO-1234yf).

In some embodiments, the present application further provideschlorinating 3,3,3-trifluoropropene to form1,1,1-trifluoro-2,3-dichloropropane (HCFC-243db). In some embodiments,chlorinating comprises reacting with chlorine or HCl/oxygen.

In some embodiments, the process of preparing HCFC-243db is thatdisclosed in WO 2015095497, which is incorporated herein by reference inits entirety.

Accordingly, in some embodiments, the process further comprisescontacting 3,3,3-trifluoropropene with chlorine in the liquid phase, inthe absence or presence of a catalyst and with or without exposure to UVlight, to form 1,1,1-trifluoro-2,3-dichloropropane (HCFC-243db).

In some embodiments, the catalyst comprises at least one metal halide,wherein the metal is a metal from Group 13, 14 or 15 of the periodictable or a transition metal or combination thereof. In some embodiments,the metal halide is supported on activated carbon. In some embodiments,the activated carbon is acid washed or caustic washed. In someembodiments, the metal is nickel, chromium, iron, scandium, yttrium,lanthanum, titanium, zirconium, hafnium, vanadium, molybdenum, tungsten,manganese, rhenium, ruthenium, osmium, cobalt, palladium, copper, zinc,tantalum, aluminum, tin, or lead. In some embodiments, the metal halideis nickel halide, iron halide or chromium halide. In some embodiments,the halide is a chloride. In some embodiments, the metal halide isnickel chloride, iron halide or chromium halide.

In some embodiments, the chlorination occurs in the vapor phase with orwithout a catalyst. In some embodiments, the chlorination is conductedat a temperature ranging from about 80° C. to about 200° C. and apressure ranging from about 10 psig to about 100 psig, with the moleratio of 3,3,3-trifluoropropene to chlorine gas ranging from about1:0.02 to about 1:1.

The present application further provides a process of preparing2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), comprisingdehydrochlorinating 1,1,1-trifluoro-2,3-dichloropropane (HCFC-243db) toform 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf).

The present application also provides a process of preparing2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), comprising reacting1,1,1-trifluoro-2,3-dichloropropane (HCFC-243db) with caustic to form2-chloro-3,3,3-trifluoropropene (HCFO-1233xf).

In some embodiments, the process of preparing HCFO-1233xf is thatdisclosed in WO 2012115957, which is incorporated herein by reference inits entirety.

Accordingly, in some embodiments, the process further comprisescontacting 1,1,1-trifluoro-2,3-dichloropropane (HCFC-243db) with acatalyst in a reaction zone to produce a product mixture comprising2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), wherein said catalystcomprises MY supported on carbon, and M is K, Na or Cs, and Y is F, Clor Br. In some embodiments, the carbon is an activated carbon. In someembodiments, the carbon is an acid washed activated carbon. In someembodiments, M is K and Y is F or Cl.

In some embodiments, the temperature in the reaction zone is from about140° C. to about 400° C. In some embodiments, the temperature in thereaction zone is from about 150° C. to about 250° C. In someembodiments, the temperature in the reaction zone is from about 175° C.to about 225° C.

In some embodiments, the product selectivity to2-chloro-3,3,3-trifluoropropene is at least 90 mole %. In someembodiments, the product selectivity to 2-chloro-3,3,3-trifluoropropeneis at least 95 mole %. In some embodiments, the dehydrochlorinationselectivity to 2-chloro-3,3,3-trifluoropropene is at least 90 mole %.

In some embodiments, the process of preparing HCFO-1233xf is thatdisclosed in US 20120215035, which is incorporated herein by referencein its entirety.

Accordingly, in some embodiments, the process further comprises1,1,1-trifluoro-2,3-dichloropropane (HCFC-243db) with a catalyst in areaction zone to produce a product mixture comprising2-chloro-3,3,3-trifluoropropene (HCFO-1233xf),

In some embodiments, the process further comprises contacting1,1,1-trifluoro-2,3-dichloropropane (HCFC-243db) with a chromiumoxyfluoride catalyst in a reaction zone to produce a product mixturecomprising 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf).

In some embodiments, the process is conducted in the presence of HF. Insome embodiments, the mole ratio of HF to2-chloro-3,3,3-trifluoropropene in the reaction zone is no more than0.9.

In some embodiments, the temperature in the reaction zone is from about200° C. to about 500° C. In some embodiments, the temperature in thereaction zone is from about 275° C. to about 450° C.

In some embodiments, the product selectivity to2-chloro-3,3,3-trifluoropropene is at least 90 mole %. In someembodiments, the dehydrochlorination selectivity to2-chloro-3,3,3-trifluoropropene is at least 95 mole %.

The present application further provides a process of preparing2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), comprisinghydrofluorinating 2-chloro-3,3,3,-trifluoropropene (HCFO-1233xf) with HFto form 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb).

In some embodiments, the process of preparing HCFC-244bb is thatdisclosed in US 20140275648, which is incorporated herein by referencein its entirety.

Accordingly, in some embodiments, the process further comprisescontacting 2-chloro-3,3,3,-trifluoropropene (HCFO-1233xf) with HF in thepresence of a fluorination catalyst in multiple reaction zones underconditions effective to produce a composition that comprises2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) and less than about 2%by weight 1,1,1,2,2-pentafluoropropane (HFC-245cb).

In some embodiments, the composition produced comprises less than about1% by weight HFC-245cb. In some embodiments, the composition producedfurther comprises less than about 5% by weight of unreacted HCFO-1233xf.In some embodiments, the composition produced further comprises lessthan about 2% by weight of unreacted HCFO-1233xf.

In some embodiments, more than about 95% of the HCFO-1233xf is convertedto HCFC-244bb. In some embodiments, more than about 98% of theHCFO-1233xf is converted to HCFC-244bb.

In some embodiments, the multiple reaction zones comprise multiplereactors operated in series. In some embodiments, the multiple reactorscomprise at lease first and second reactors operated in series.

In some embodiments, the fluorination catalyst is selected from thegroup consisting of Lewis acids, transition metal halides, transitionmetal oxides, Group IVb metal halides, a Group Vb metal halides, orcombinations thereof. In some embodiments, the fluorination catalyst isselect from the group consisting of SbCl₅, SbCl₃, SbF₅, SnCl₄, TaCl₅,TiCl₄, NbCl₅, MoCl₆, FeCl₃, a fluorinated species of SbCl₅, afluorinated species of SbCl₃, a fluorinated species of SnCl₄, afluorinated species of TaCl₅, a fluorinated species of TiCl₄, afluorinated species of NbCl₅, a fluorinated species of MoCl₆, afluorinated species of FeCl₃, or combinations thereof.

In some embodiments, the fluorination catalyst is the same or differentin each of the multiple reaction zones.

In another embodiment, the process further comprises:

a) contacting, in a first reaction zone, feed2-chloro-3,3,3,-trifluoropropene (HCFO-1233xf) with HF and firstfluorination catalyst under conditions effective to produce a firstcomposition comprising unreacted HCFO-1233xf, a first amount of2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), and a first amount of1,1,1,2,2-pentafluoropropane (HFC-245cb);

b) contacting, in a second reaction zone, the first composition with asecond fluorination catalyst under conditions to produce a secondcomposition, wherein the second composition comprises HCFC-244bb, andless than about 5% HCFO-1233xf by weight relative to the amount of feed1233xf, and less than about 2% by weight HFO-245cb.

In some embodiments, the second reaction zone is comprised of one ormore reactors operated in series. In some embodiments, the first and thesecond reaction zones each comprise CSTR reactors. In some embodiments,said first composition further comprises carryover first fluorinationcatalyst which is removed from the first composition prior to contactingin said second reaction zone. In some embodiments, the first and secondfluorination catalysts each comprise a fluorinated SbCl₅ species.

The present application further provides a process of preparing2,3,3,3-tetrafluoropropene (HFO-1234yf), comprising hydrofluorinating2-chloro-3,3,3,-trifluoropropene (HCFO-1233xf) with HF to form2,3,3,3-tetrafluoropropene (HFO-1234yf).

The present application also provides a process of preparing2,3,3,3-tetrafluoropropene (HFO-1234yf), comprising dehydrochlorinating2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) to form2,3,3,3-tetrafluoropropene (HFO-1234yf).

The present application additionally provides a process of preparing2,3,3,3-tetrafluoropropene (HFO-1234yf), comprising reacting2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) with caustic to form2,3,3,3-tetrafluoropropene (HFO-1234yf).

In some embodiments, the process of preparing HFO-1234yf is thatdisclosed in US 20140350309, which is incorporated herein by referencein its entirety.

Accordingly, in some embodiments, the process further comprises: (a)removing impurities from a reactor such that the reactor issubstantially free of impurities; (b) providing a starting compositioncomprising 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) in thereactor under conditions effective to produce a final compositioncomprising 2,3,3,3-tetrafluoropropene (HFO-1234yf).

In some embodiments, the impurities in the reactor are selected from thegroup consisting of metal halides, metal oxides, and carbonaceousmaterials. In some embodiments, the metal halides comprise halides ofNi, Cr, Fe, Mo, Nb, Cu, and Co.

In some embodiments, the step of removing impurities from the reactorcomprises introducing a reducing agent into the reactor under conditionseffective to convert any metal halides or metal oxides into metallicmetals.

In some embodiments, the reducing agent is selected from the groupconsisting of H₂, NH₃, CO, C₁-C₁₂ hydrocarbons, and combinations ofthese.

In some embodiments, the step of removing impurities from the reactorcomprises introducing an oxidizing agent into the reactor underconditions effective to burn off the carbonaceous materials in thereactor.

In some embodiments, the oxidizing agent is selected from the groupconsisting of H₂O, CO₂, O₂, air, O₃, Cl₂, N₂O, and combinations ofthese. In some embodiments, the oxidizing agent comprises oxygen.

In some embodiments, the step of removing impurities from the reactorcomprises physically removing carbonaceous materials, metal oxides, andmetal halides from the reactor. In some embodiments, the step ofphysically removing the carbonaceous materials, metal oxides, and metalhalides from the reactor is selected from the group consisting ofelectrical polishing, mechanical polishing, hydraulic methods, andcombinations of these.

In some embodiments, the selectivity to 2,3,3,3-tetrafluoropropene is atleast 90% or higher.

In some embodiments, the process provided here further comprises: (a)providing a starting composition comprising2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) in a reactor that issubstantially free from impurities; and (b) contacting the startingcomposition in the reactor under conditions effective to produce a finalcomposition comprising 2,3,3,3-tetrafluoropropene (HFO-1234yf).

In some embodiments, the selectivity to 2,3,3,3-tetrafluoropropene is atleast 90% or higher.

In some embodiments, the process of preparing HFO-1234yf is thatdisclosed in US 20140303409, which is incorporated herein by referencein its entirety.

Accordingly, in some embodiments, the process further comprises: (i)providing a composition comprising 2-chloro-1,1,1,2-tetrafluoropropane(HCFC-244bb); (ii) reducing the level of HF within the composition suchthat it is substantially free of HF; and (iii) contacting said startingcomposition with a dehydrochlorination catalyst to produce a finalcomposition comprising 2,3,3,3-tetrafluoropropene (HFO-1234yf).

In some embodiments, the level of HF is reduced within the compositionsuch that HF is present in the composition in an amount less than about500 ppm. In some embodiments, the level of HF is reduced within thecomposition such that HF is present in the composition in an amount lessthan about 50 ppm. In some embodiments, reducing the HF level of thecomposition comprises the distilling of the HF, passing the compositionthrough a scrubber, or passing the composition over a solid sorbent.

In some embodiments, the solid sorbent is selected from the groupconsisting of alumina, calcium carbonate, sodium carbonate, and sodiumaluminate.

The present application further provides a process, comprising (i)providing a starting composition comprising a2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) that is substantiallyfree of HF; and (ii) contacting said starting composition with adehydrochlorination catalyst to produce a final composition comprising2,3,3,3-tetrafluoropropene (HFO-1234yf).

In some embodiments, the HF is present in the composition in an amountless than about 500 ppm. In some embodiments, the HF is present in thecomposition in an amount less than about 50 ppm.

In some embodiments, the contacting of said starting composition with adehydrochlorination catalyst occurs in the vapor phase. In someembodiments, the contacting of said starting composition with adehydrochlorination catalyst occurs in the liquid phase.

In some embodiments, the catalyst is selected from the group consistingof (i) one or more metal halides, (ii) one or more halogenated metaloxides, (iii) one or more zero-valent metals/metal alloys, and (iv) acombination of two or more of these.

In some embodiments, the dehydrochlorinating occurs in the vapor phase.

In some embodiments, the intermediate products made in each step arepurified before reacting in the next step so that impurities in the1234yf made in the final step can be removed to achieve the desiredpurity, for example >99.5% by weight. Purification techniques known inthe art such as distillation, extraction, decantation, and adsorptioncan be used. One skilled in the art will recognize that impurities thatare advantageous to remove before the final reaction step to make 1234yfare those that have, or react to form those that have, similar boilingpoints to 1234yf.

In some embodiments, the processes provided herein further comprisesubstantially isolating the 3,3,3-trifluoroprop-1-ene (i.e., 1243zf). By“substantially isolated” is meant that the compound is at leastpartially or substantially separated from the environment in which itwas formed or detected. Partial separation can include, for example, acomposition enriched in the compounds provided herein. Substantialseparation can include compositions containing at least about 50%, atleast about 60%, at least about 70%, at least about 80%, at least about90%, at least about 95%, at least about 97%, or at least about 99% byweight of the compounds provided herein, or salt thereof. Methods forisolating compounds are routine in the art.

In some embodiments, the processes provided herein further comprisesubstantially isolating (e.g., purifying) 3,3,3-trifluoroprop-1-ene viadistillation. In some embodiments, the process comprises substantiallyisolating the 3,3,3-trifluoroprop-1-ene by removing one or moreadditional components of a reaction mixture (e.g., 253fb, 1233xf, 254fb,or any combination thereof). In some embodiments, the one or moreadditional components of the reaction mixture are removed viadistillation.

Uses

The processes provided herein are useful for preparing3,3,3-trifluoroprop-1-ene (HFO-1234zf), a compound which may be usefulin the manufacture of silicones used as hydraulic fluids or as anintermediate for producing 2,3,3,3-tetrafluoroprop-1-ene (HFO-1234yf).HFO-1234yf is useful for a wide variety of applications, such asrefrigerants, uses in high-temperature heat pumps, organic Rankinecycles, as fire extinguishing/fire suppression agents, propellants, foamblowing agents, solvents, and/or cleaning fluids.

Compositions

The present application further provides compositions comprising one ormore major components (e.g., 3,3,3-trifluoroprop-1-ene,3-chloro-1,1,1-trifluoropropane, or a mixture thereof) in combinationwith one or more additional compounds. In some embodiments, thecompositions are prepared according to one or more of the processesdescribed herein.

The additional compounds of the compositions described herein mayprovide improved solubility for active ingredients in an aerosol orpolymer constituents of a foam. Additionally, for refrigerantapplications, such as use in air conditioning, heat pumps,refrigeration, and power cycles (e.g., organic Rankine cycles), theadditional compounds may provide improved solubility with refrigerationlubricants, such as mineral oils, alkylbenzenes, synthetic paraffins,synthetic naphthenes, poly(alpha)olefins, polyol esters (POE),polyalkylene glycols (PAG), polyvinyl ethers (PVE), orperfluoropolyethers (PFPE), or mixtures thereof. Further, the presenceof the additional compounds in a sample of 3,3,3-trifluoroprop-1-ene,3-chloro-1,1,1-trifluoropropane, or a mixture thereof, may be used toidentify the process by which one or more of the major components wasmanufactured.

Accordingly, the present application provides a composition comprising:

i) 3-chloro-1,1,1-trifluoropropane (253fb); and

ii) one or more additional compounds selected from the group consistingof 3,3,3-trifluoroprop-1-ene (1243zf), 2-chloro-3,3,3-trifluoropropene(1233xf), 1,1,1,3-tetrafluoropropane (254fb), and1,1,1-trifluoro-2,3-dichloropropane (243db).

In some embodiments, the composition consists essentially of:

i) 3-chloro-1,1,1-trifluoropropane (253fb); and

ii) one or more additional compounds selected from the group consistingof 3,3,3-trifluoroprop-1-ene (1243zf), 2-chloro-3,3,3-trifluoropropene(1233xf), 1,1,1,3-tetrafluoropropane (254fb), and1,1,1-trifluoro-2,3-dichloropropane (243db).

In some embodiments, the compositions provided herein are substantiallyfree of a catalyst (e.g., a phase transfer catalyst) described herein.

In some embodiments, the compositions provided herein further comprise acatalyst described herein. In some embodiments, the catalyst is a phasetransfer catalyst described herein.

In some embodiments, the composition comprises about 25 mole percent orless 3-chloro-1,1,1-trifluoropropane (253fb), for example, about 20 molepercent or less, about 15 mole percent or less, about 10 mole percent orless, about 5 mole percent or less, about 2 mole percent or less, orabout 1 mole percent or less 3-chloro-1,1,1-trifluoropropane (253fb).

In some embodiments, the composition comprises about 1 to about 25 molepercent 3-chloro-1,1,1-trifluoropropane.

In some embodiments, the composition comprises about 1 to about 5 molepercent 3-chloro-1,1,1-trifluoropropane.

In some embodiments, the composition comprises about 1 to about 2 molepercent 3-chloro-1,1,1-trifluoropropane.

In some embodiments, the composition comprises about 20 to about 25 molepercent 3-chloro-1,1,1-trifluoropropane.

In some embodiments, the composition comprises about 23 to about 25 molepercent 3-chloro-1,1,1-trifluoropropane.

In some embodiments, the composition comprises about 70 mole percent orgreater 3,3,3-trifluoroprop-1-ene (1243zf), for example, about 75 molepercent or greater, about 80 mole percent or greater, about 85 molepercent or greater, about 90 mole percent or greater, about 95 molepercent or greater, about 96 mole percent or greater, about 97 molepercent or greater, about 98 mole percent or greater, about 99 molepercent or greater, about 99.5 mole percent or greater, about 99.6 molepercent or greater, about 99.7 mole percent or greater, about 99.8 molepercent or greater, or about 99.9 mole percent or greater3,3,3-trifluoroprop-1-ene.

In some embodiments, the composition comprises about 70 to about 80 molepercent 3,3,3-trifluoroprop-1-ene.

In some embodiments, the composition comprises about 74 to about 76 molepercent 3,3,3-trifluoroprop-1-ene.

In some embodiments, the composition comprises about 95 to about 99.9mole percent 3,3,3-trifluoroprop-1-ene.

In some embodiments, the composition comprises about 98 to about 99 molepercent 3,3,3-trifluoroprop-1-ene.

In some embodiments, the composition comprises about 25 percent or less3-chloro-1,1,1-trifluoropropane (253fb) as measured by gaschromatography/mass spectrometry (GC-MS) (e.g., % area under the curve),for example, about 20 percent or less, about 15 percent or less, about10 percent or less, about 5 percent or less, about 2 percent or less, orabout 1 percent or less 3-chloro-1,1,1-trifluoropropane (253fb) asmeasured by GC-MS.

In some embodiments, the composition comprises about 1 to about 25percent 3-chloro-1,1,1-trifluoropropane as measured by GC-MS.

In some embodiments, the composition comprises about 1 to about 5percent 3-chloro-1,1,1-trifluoropropane as measured by GC-MS.

In some embodiments, the composition comprises about 1 to about 2percent 3-chloro-1,1,1-trifluoropropane as measured by GC-MS.

In some embodiments, the composition comprises about 20 to about 25percent 3-chloro-1,1,1-trifluoropropane as measured by GC-MS.

In some embodiments, the composition comprises about 23 to about 25percent 3-chloro-1,1,1-trifluoropropane as measured by GC-MS.

In some embodiments, the composition comprises about 70 percent orgreater 3,3,3-trifluoroprop-1-ene (1243zf) as measured by GC-MS, forexample, about 75 percent or greater, about 80 percent or greater, about85 percent or greater, about 90 percent or greater, about 95 percent orgreater, about 96 percent or greater, about 97 percent or greater, about98 percent or greater, about 99 percent or greater, about 99.5 percentor greater, about 99.6 percent or greater, about 99.7 percent orgreater, about 99.8 percent or greater, or about 99.9 percent or greater3,3,3-trifluoroprop-1-ene as measured by GC-MS.

In some embodiments, the composition comprises about 70 to about 80percent 3,3,3-trifluoroprop-1-ene as measured by GC-MS.

In some embodiments, the composition comprises about 74 to about 76percent 3,3,3-trifluoroprop-1-ene as measured by GC-MS.

In some embodiments, the composition comprises about 95 to about 99.9percent 3,3,3-trifluoroprop-1-ene as measured by GC-MS.

In some embodiments, the composition comprises about 98 to about 99percent 3,3,3-trifluoroprop-1-ene as measured by GC-MS.

In some embodiments, the composition comprises about 0.5 mole percent orless 2-chloro-3,3,3-trifluoropropene (1233xf), for example, about 0.4mole percent or less, about 0.3 mole percent or less, about 0.2 molepercent or less, or about 0.1 mole percent or less2-chloro-3,3,3-trifluoropropene.

In some embodiments, the composition comprises about 0.01 to about 0.15mole percent 2-chloro-3,3,3-trifluoropropene.

In some embodiments, the composition comprises about 0.05 to about 0.15mole percent 2-chloro-3,3,3-trifluoropropene.

In some embodiments, the composition comprises about 0.05 to about 0.2mole percent 2-chloro-3,3,3-trifluoropropene.

In some embodiments, the composition comprises about 0.05 to about 0.1mole percent 2-chloro-3,3,3-trifluoropropene.

In some embodiments, the composition comprises about 0.05 to about 0.07mole percent 2-chloro-3,3,3-trifluoropropene.

In some embodiments, the composition comprises about 0.1 to about 0.2mole percent 2-chloro-3,3,3-trifluoropropene.

In some embodiments, the composition comprises about 0.14 to about 0.16mole percent 2-chloro-3,3,3-trifluoropropene.

In some embodiments, the composition comprises about 0.1 mole percent orless 1,1,1,3-tetrafluoropropane (254fb), for example, 0.075 mole percentor less, 0.05 mole percent or less, 0.025 mole percent or less, or 0.01mole percent or less 1,1,1,3-tetrafluoropropane.

In some embodiments, the composition comprises about 0.01 to about 0.1mole percent 1,1,1,3-tetrafluoropropane.

In some embodiments, the composition comprises about 0.01 to about 0.05mole percent 1,1,1,3-tetrafluoropropane.

In some embodiments, the composition comprises about 0.01 to about 0.02mole percent 1,1,1,3-tetrafluoropropane.

In some embodiments, the composition comprises about 0.5 percent or less2-chloro-3,3,3-trifluoropropene (1233xf) as measured by GC-MS, forexample, about 0.4 percent or less, about 0.3 percent or less, about 0.2percent or less, or about 0.1 percent or less2-chloro-3,3,3-trifluoropropene as measured by GC-MS.

In some embodiments, the composition comprises about 0.01 to about 0.15percent 2-chloro-3,3,3-trifluoropropene as measured by GC-MS.

In some embodiments, the composition comprises about 0.05 to about 0.15percent 2-chloro-3,3,3-trifluoropropene as measured by GC-MS.

In some embodiments, the composition comprises about 0.05 to about 0.2percent 2-chloro-3,3,3-trifluoropropene as measured by GC-MS.

In some embodiments, the composition comprises about 0.05 to about 0.1percent 2-chloro-3,3,3-trifluoropropene as measured by GC-MS.

In some embodiments, the composition comprises about 0.05 to about 0.07percent 2-chloro-3,3,3-trifluoropropene as measured by GC-MS.

In some embodiments, the composition comprises about 0.1 to about 0.2percent 2-chloro-3,3,3-trifluoropropene as measured by GC-MS.

In some embodiments, the composition comprises about 0.14 to about 0.16percent 2-chloro-3,3,3-trifluoropropene as measured by GC-MS.

In some embodiments, the composition comprises about 0.1 percent or less1,1,1,3-tetrafluoropropane (254fb) as measured by GC-MS, for example,0.075 percent or less, 0.05 percent or less, 0.025 percent or less, or0.01 percent or less 1,1,1,3-tetrafluoropropane as measured by GC-MS.

In some embodiments, the composition comprises about 0.01 to about 0.1percent 1,1,1,3-tetrafluoropropane as measured by GC-MS.

In some embodiments, the composition comprises about 0.01 to about 0.05percent 1,1,1,3-tetrafluoropropane as measured by GC-MS.

In some embodiments, the composition comprises about 0.01 to about 0.02percent 1,1,1,3-tetrafluoropropane as measured by GC-MS.

In some embodiments, the composition comprises3-chloro-1,1,1-trifluoropropane (253fb), 3,3,3-trifluoroprop-1-ene(1243zf), 1,1,1-trifluoro-2,3-dichloropropane (243db),2-chloro-3,3,3-trifluoropropene (1233xf).

In some embodiments, the composition comprises3-chloro-1,1,1-trifluoropropane (253fb), 3,3,3-trifluoroprop-1-ene(1243zf), 1,1,1,3-tetrafluoropropane (254fb), and2-chloro-3,3,3-trifluoropropene (1233xf).

In some embodiments, the composition comprises3-chloro-1,1,1-trifluoropropane (253fb), 3,3,3-trifluoroprop-1-ene(1243zf), and 2-chloro-3,3,3-trifluoropropene (1233xf).

In some embodiments, the composition comprises3-chloro-1,1,1-trifluoropropane (253fb) and1,1,1-trifluoro-2,3-dichloropropane (243db).

In some embodiments, the composition comprises3-chloro-1,1,1-trifluoropropane (253fb),1,1,1-trifluoro-2,3-dichloropropane (243db), and a catalyst. In someembodiments, the catalyst is a phase transfer catalyst described herein.

In some embodiments, the composition comprises:

about 70 to about 80 mole percent 3,3,3-trifluoroprop-1-ene;

about 20 to about 25 mole percent 3-chloro-1,1,1-trifluoropropane;

about 0.05 to about 0.1 mole percent 2-chloro-3,3,3-trifluoropropene;and

about 0.01 to about 0.05 mole percent 1,1,1,3-tetrafluoropropane.

In some embodiments, the composition comprises:

about 74 to about 76 mole percent 3,3,3-trifluoroprop-1-ene;

about 23 to about 25 mole percent 3-chloro-1,1,1-trifluoropropane;

about 0.05 to about 0.07 mole percent 2-chloro-3,3,3-trifluoropropene;and

about 0.01 to 0.02 mole percent 1,1,1,3-tetrafluoropropane.

In some embodiments, the composition comprises:

about 95 to about 99 mole percent 3,3,3-trifluoroprop-1-ene;

about 1 to about 2 mole percent 3-chloro-1,1,1-trifluoropropane; and

about 0.1 to about 0.2 mole percent 2-chloro-3,3,3-trifluoropropene.

In some embodiments, the composition comprises:

about 98 to about 99 mole percent 3,3,3-trifluoroprop-1-ene;

about 1 to about 2 mole percent 3-chloro-1,1,1-trifluoropropane; and

about 0.1 to about 0.2 mole percent 2-chloro-3,3,3-trifluoropropene.

In some embodiments, the composition comprises:

about 70 to about 80 percent 3,3,3-trifluoroprop-1-ene;

about 20 to about 25 percent 3-chloro-1,1,1-trifluoropropane;

about 0.05 to about 0.1 percent 2-chloro-3,3,3-trifluoropropene; and

about 0.01 to about 0.05 mole percent 1,1,1,3-tetrafluoropropane asmeasured by GC-MS.

In some embodiments, the composition comprises:

about 74 to about 76 percent 3,3,3-trifluoroprop-1-ene;

about 23 to about 25 percent 3-chloro-1,1,1-trifluoropropane;

about 0.05 to about 0.07 percent 2-chloro-3,3,3-trifluoropropene; and

about 0.01 to 0.02 percent 1,1,1,3-tetrafluoropropane as measured byGC-MS.

In some embodiments, the composition comprises:

about 95 to about 99 percent 3,3,3-trifluoroprop-1-ene;

about 1 to about 2 percent 3-chloro-1,1,1-trifluoropropane; and

about 0.1 to about 0.2 percent 2-chloro-3,3,3-trifluoropropene asmeasured by GC-MS.

In some embodiments, the composition comprises:

about 98 to about 99 percent 3,3,3-trifluoroprop-1-ene;

about 1 to about 2 percent 3-chloro-1,1,1-trifluoropropane; and

about 0.1 to about 0.2 percent 2-chloro-3,3,3-trifluoropropene asmeasured by GC-MS.

EXAMPLES

The invention will be described in greater detail by way of specificexamples. The following examples are offered for illustrative purposes,and are not intended to limit the invention in any manner.

Example 1. 253fb Dehydrochlorination by NaOH without Phase TransferCatalyst in a 400 mL Stirred Autoclave Reactor at 60° C. with 1000 RPMAgitation Rate

A 12 wt % NaOH solution in water (195 g) and3-chloro-1,1,1-trifluoropropane (i.e., 253fb; 10 g) were charged into a400 mL autoclave and heated to 60° C. The reaction mixture was agitatedat 1000 RPM (estimated to be the equivalent of 10.1 HP per 1000 gallons)at 60° C. The pressure increased continuously from 7 psig to 78 psig inabout 2.5 hours which indicated the progress of reaction. After pressureof reactor stabilized, the reaction mixture was stirred for another 1.5hours. The product was analyzed by GC/MS as shown in Table 1, andanalysis showed ˜98.5% of 253fb was converted to3,3,3-trifluoroprop-1-ene (i.e., 1243zf) without use of a phase transfercatalyst.

TABLE 1 Compounds GC area (%) 1243zf 98.4515 253fb 1.3459 1233xf 0.1542other 0.0484

Example 2. 253fb Dehydrochlorination by NaOH without Phase TransferCatalyst in a 400 mL Stirred Autoclave Reactor at 40° C. with 1000 RPMAgitation Rate

A 12 wt % NaOH solution in water (195 g) and 253fb (10 g) were chargedinto a 400 mL autoclave and heated to 60° C. The reaction mixture wasagitated at 1000 rpm (10.1 HP per 1000 gallons) at 40° C. The pressureincreased continuously from 9 psig to 27 psig in about 3.5 hours whichindicated the progress of reaction. The product was analyzed by GC/MS asshown in Table 2, and analysis showed ˜75.4% of 253fb was converted to1243zf without use of a phase transfer catalyst.

TABLE 2 Compounds GC area (%) 1243zf 75.4423 253fb 24.4328 1233xf 0.0652254fb 0.0127 other 0.0484

Other Embodiments

1. In some embodiments, the present application provides a process ofpreparing 3,3,3-trifluoroprop-1-ene, comprising reacting3-chloro-1,1,1-trifluoropropane with a base in an aqueous solventcomponent, wherein the reacting is conducted in the absence of a phasetransfer catalyst, wherein the aqueous solvent component comprises 0 to40% w/w of an organic solvent.

2. The process of embodiment 1, wherein the aqueous solvent componentdoes not comprise an organic solvent.

3. The process of embodiment 1 or 2, wherein the base is an aqueousbase.

4. The process of embodiment 3, wherein the base is a metal hydroxidebase, a metal carbonate base, a metal phosphate base, or a metalfluoride base.

5. The process of embodiment 3, wherein the base is NaOH, KOH, LiOH,CsOH, Ca(OH)₂, Zn(OH)₂, Na₂CO₃, K₂CO₃, K₃PO₄, Na₃PO₄, KF, or CsF.

6. The process of embodiment 3, wherein the base is KOH or NaOH.

7. The process of embodiment 3, wherein the base is NaOH.

8. The process of any one of embodiments 1-7, wherein about 0.01 toabout 5 molar equivalents of base is used based on one molar equivalentof 3-chloro-1,1,1-trifluoropropane.

9. The process of any one of embodiments 1-8, wherein the reacting isconducted at a temperature of from about 20° C. to about 100° C.

10. The process of any one of embodiments 1-8, wherein the reacting isconducted at a temperature of from about 35° C. to about 80° C.

11. The process of any one of embodiments 1-10, wherein the reacting isconducted at a pressure of about −10 psig to about 500 psig.

12. The process of any one of embodiments 1-10, wherein the reacting isconducted at a pressure of about 5 psig to about 230 psig.

13. The process of any one of embodiments 1-10, wherein the reacting isconducted at a pressure of about 5 psig to about 150 psig.

14. The process of any one of embodiments 1-13, wherein the reactingcomprises mixing the 3-chloro-1,1,1-trifluoropropane and base with amixing power of from about 0.1 to about 50 horsepower per 1000 gallonsof the reaction mixture.

15. The process of any one of embodiments 1-13, wherein the reactingcomprises mixing the 3-chloro-1,1,1-trifluoropropane and base with amixing power ranging from about 0.5 horsepower to about 40 horsepowerper 1000 gallons of the reaction mixture.

16. The process of any one of embodiments 1-8, wherein the reacting isconducted at a temperature of from about 35° C. to about 80° C. and at apressure of about 5 psig to about 230 psig.

17. The process of any one of embodiments 1-8, wherein the reacting isconducted at a temperature of from about 35° C. to about 80° C. and at apressure of about 5 psig to about 150 psig.

18. The process of any one of embodiments 1-18, wherein the reactionfurther comprises an amine.

19. The process of any one of embodiments 1-18, wherein the3-chloro-1,1,1-trifluoropropane is prepared by a process comprisingreacting 1,1,1,3-tetrachloropropane with hydrofluoric acid.

20. The process of any one of embodiments 1-19, further comprisingchlorinating 3,3,3-trifluoropropene to form1,1,1-trifluoro-2,3-dichloropropane (HCFC-243db).

21. The process of embodiment 20, wherein said chlorinating comprisesreacting with chlorine or HCl/oxygen.

22. The process of any one of embodiments 20-21, comprisingdehydrochlorinating 1,1,1-trifluoro-2,3-dichloropropane (HCFC-243db) toform 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf).

23. The process of embodiments 22, comprising reacting the1,1,1-trifluoro-2,3-dichloropropane (HCFC-243db) with caustic to form2-chloro-3,3,3-trifluoropropene (HCFO-1233xf).

24. The process of any one of embodiments 22-23, further comprisinghydrofluorinating 2-chloro-3,3,3,-trifluoropropene (HCFO-1233xf) with HFto form 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb).

25. The process of any one of embodiments 22-23, further comprisinghydrofluorinating 2-chloro-3,3,3,-trifluoropropene (HCFO-1233xf) with HFto form 2,3,3,3-tetrafluoropropene (HFO-1234yf).

26. The process of embodiment 24, further comprising dehydrochlorinating2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) to form2,3,3,3-tetrafluoropropene (HFO-1234yf).

27. The process of embodiments 24, further comprising reacting2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) with caustic to form2,3,3,3-tetrafluoropropene (HFO-1234yf).

28. A process of preparing 3,3,3-trifluoroprop-1-ene comprising reacting3-chloro-1,1,1-trifluoropropane with aqueous NaOH, wherein the reactingis performed at a temperature of from about 35° C. to about 80° C. andat a pressure of from about 5 psig to about 230 psig, and wherein thereacting is conducted in the absence of a phase transfer catalyst and anorganic solvent component.

29. The process of embodiments 28, wherein the reacting is conducted ata pressure of from about 5 psig to about 150 psig.

30. The process of embodiments 28 or 29, wherein the3-chloro-1,1,1-trifluoropropane is prepared by reacting1,1,1,3-tetrachloropropane with hydrofluoric acid.

31. A process of preparing a mixture of 3,3,3-trifluoroprop-1-ene(HFO-1243zf) and 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf),comprising reacting a mixture of 3-chloro-1,1,1-trifluoropropane(HCFC-253fb) and 1,1,1-trifluoro-2,3-dichloropropane (HCFC-243db) with abase in an aqueous solvent component, wherein the reacting is conductedin the absence of a phase transfer catalyst, wherein the aqueous solventcomponent comprises 0 to 40% of an organic solvent.

32. The process of embodiment 31, wherein the aqueous solvent componentdoes not comprise an organic solvent.

33. A composition comprising:

i) 3-chloro-1,1,1-trifluoropropane (253fb); and

ii) one or more additional compounds selected from the group consistingof 3,3,3-trifluoroprop-1-ene (1243zf), 2-chloro-3,3,3-trifluoropropene(1233xf), 1,1,1,3-tetrafluoropropane (254fb), and1,1,1-trifluoro-2,3-dichloropropane (243db).

34. The composition of embodiment 33, wherein the composition comprises3-chloro-1,1,1-trifluoropropane (253fb), 3,3,3-trifluoroprop-1-ene(1243zf), and 2-chloro-3,3,3-trifluoropropene (1233xf).

35. The composition of embodiment 33 or 34, wherein the compositioncomprises:

about 95 to about 99 percent 3,3,3-trifluoroprop-1-ene (1243zf);

about 1 to about 2 percent 3-chloro-1,1,1-trifluoropropane (253fb); and

about 0.1 to about 0.2 percent 2-chloro-3,3,3-trifluoropropene (1233xf),as measured by GC-MS.

36. The composition of embodiment 33 or 34, wherein the compositioncomprises:

about 98 to about 99 percent 3,3,3-trifluoroprop-1-ene (1243zf);

about 1 to about 2 percent 3-chloro-1,1,1-trifluoropropane (253fb); and

about 0.1 to about 0.2 percent 2-chloro-3,3,3-trifluoropropene (1233xf),as measured by GC-MS.

37. The composition of embodiment 33, wherein the composition comprises3-chloro-1,1,1-trifluoropropane (253fb), 3,3,3-trifluoroprop-1-ene(1243zf), 1,1,1,3-tetrafluoropropane (254fb), and2-chloro-3,3,3-trifluoropropene (1233xf).

38. The composition of embodiments 33 or 37, wherein the compositioncomprises:

about 70 to about 80 percent 3,3,3-trifluoroprop-1-ene (1243zf);

about 20 to about 25 percent 3-chloro-1,1,1-trifluoropropane (253fb);

about 0.05 to about 0.1 percent 2-chloro-3,3,3-trifluoropropene(1233xf); and

about 0.01 to about 0.05 percent 1,1,1,3-tetrafluoropropane (254fb), asmeasured by GC-MS.

39. The composition of embodiments 33 or 37, wherein the compositioncomprises:

about 74 to about 76 mole percent 3,3,3-trifluoroprop-1-ene (1243zf);

about 23 to about 25 mole percent 3-chloro-1,1,1-trifluoropropane(253fb);

about 0.05 to about 0.07 mole percent 2-chloro-3,3,3-trifluoropropene(1233xf); and

about 0.01 to 0.02 mole percent 1,1,1,3-tetrafluoropropane (254fb), asmeasured by GC-MS.

40. The composition of embodiment 33, wherein the composition comprises3-chloro-1,1,1-trifluoropropane (253fb), 3,3,3-trifluoroprop-1-ene(1243zf), 1,1,1-trifluoro-2,3-dichloropropane (243db), and2-chloro-3,3,3-trifluoropropene (1233xf).

41. The composition of embodiment 33, wherein the composition comprises3-chloro-1,1,1-trifluoropropane (253fb),1,1,1-trifluoro-2,3-dichloropropane (243db).

42. The composition of any one of embodiments 33 to 41, wherein thecomposition further comprises a catalyst.

43. The composition of any one of embodiments 33 to 41, wherein thecomposition is substantially free of a catalyst.

It is to be understood that while the invention has been described inconjunction with the detailed description thereof, the foregoingdescription is intended to illustrate and not limit the scope of theinvention, which is defined by the scope of the appended claims. Otheraspects, advantages, and modifications are within the scope of thefollowing claims. It should be appreciated by those persons havingordinary skill in the art(s) to which the present invention relates thatany of the features described herein in respect of any particular aspectand/or embodiment of the present invention can be combined with one ormore of any of the other features of any other aspects and/orembodiments of the present invention described herein, withmodifications as appropriate to ensure compatibility of thecombinations. Such combinations are considered to be part of the presentinvention contemplated by this disclosure.

1. A process of preparing 3,3,3-trifluoroprop-1-ene, comprising reacting3-chloro-1,1,1-trifluoropropane with a base in an aqueous solventcomponent, wherein the reacting is conducted in the absence of a phasetransfer catalyst, wherein the aqueous solvent component comprises 0 to40% w/w of an organic solvent.
 2. The process of claim 1, wherein theaqueous solvent component does not comprise an organic solvent.
 3. Theprocess of claim 1, wherein the base is an aqueous base.
 4. The processof claim 3, wherein the base is a metal hydroxide base, a metalcarbonate base, a metal phosphate base, or a metal fluoride base.
 5. Theprocess of claim 3, wherein the base is NaOH, KOH, LiOH, CsOH, Ca(OH)₂,Zn(OH)₂, Na₂CO₃, K₂CO₃, K₃PO₄, Na₃PO₄, KF, or CsF.
 6. The process ofclaim 3, wherein the base is KOH or NaOH.
 7. (canceled)
 8. The processof claim 1, wherein about 0.01 to about 5 molar equivalents of base isused based on one molar equivalent of 3-chloro-1,1,1-trifluoropropane.9. The process of claim 1, wherein the reacting is conducted at atemperature of from about 20° C. to about 100° C.
 10. (canceled)
 11. Theprocess of claim 1, wherein the reacting is conducted at a pressure ofabout −10 psig to about 500 psig. 12-13. (canceled)
 14. The process ofclaim 1, wherein the reacting comprises mixing the3-chloro-1,1,1-trifluoropropane and base with a mixing power of fromabout 0.1 to about 50 horsepower per 1000 gallons of the reactionmixture.
 15. (canceled)
 16. The process of claim 1, wherein the reactingis conducted at a temperature of from about 35° C. to about 80° C. andat a pressure of about 5 psig to about 230 psig.
 17. (canceled)
 18. Theprocess of claim 1, wherein the reaction further comprises an amine. 19.The process of claim 1, wherein the 3-chloro-1,1,1-trifluoropropane isprepared by a process comprising reacting 1,1,1,3-tetrachloropropanewith hydrofluoric acid.
 20. The process of claim 1, further comprisingchlorinating 3,3,3-trifluoropropene to form1,1,1-trifluoro-2,3-dichloropropane (HCFC-243db).
 21. The process ofclaim 20, wherein said chlorinating comprises reacting with chlorine orHCl/oxygen.
 22. The process of claim 20, comprising dehydrochlorinating1,1,1-trifluoro-2,3-dichloropropane (HCFC-243db) to form2-chloro-3,3,3-trifluoropropene (HCFO-1233xf).
 23. The process of claim22, comprising reacting the 1,1,1-trifluoro-2,3-dichloropropane(HCFC-243db) with caustic to form 2-chloro-3,3,3-trifluoropropene(HCFO-1233xf).
 24. The process of claim 22, further comprisinghydrofluorinating 2-chloro-3,3,3,-trifluoropropene (HCFO-1233xf) with HFto form 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb).
 25. Theprocess of claim 22, further comprising hydrofluorinating2-chloro-3,3,3,-trifluoropropene (HCFO-1233xf) with HF to form2,3,3,3-tetrafluoropropene (HFO-1234yf).
 26. The process of claim 24,further comprising dehydrochlorinating2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) to form2,3,3,3-tetrafluoropropene (HFO-1234yf).
 27. The process of claim 24,further comprising reacting 2-chloro-1,1,1,2-tetrafluoropropane(HCFC-244bb) with caustic to form 2,3,3,3-tetrafluoropropene(HFO-1234yf).
 28. A process of preparing 3,3,3-trifluoroprop-1-enecomprising reacting 3-chloro-1,1,1-trifluoropropane with aqueous NaOH,wherein the reacting is performed at a temperature of from about 35° C.to about 80° C. and at a pressure of from about 5 psig to about 230psig, and wherein the reacting is conducted in the absence of a phasetransfer catalyst and an organic solvent component. 29-30. (canceled)31. A process of preparing a mixture of 3,3,3-trifluoroprop-1-ene(HFO-1243zf) and 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf),comprising reacting a mixture of 3-chloro-1,1,1-trifluoropropane(HCFC-253fb) and 1,1,1-trifluoro-2,3-dichloropropane (HCFC-243db) with abase in an aqueous solvent component, wherein the reacting is conductedin the absence of a phase transfer catalyst, wherein the aqueous solventcomponent comprises 0 to 40% of an organic solvent.
 32. (canceled)
 33. Acomposition comprising: i) 3-chloro-1,1,1-trifluoropropane (253fb); andii) one or more additional compounds selected from the group consistingof 3,3,3-trifluoroprop-1-ene (1243zf), 2-chloro-3,3,3-trifluoropropene(1233xf), 1,1,1,3-tetrafluoropropane (254fb), and1,1,1-trifluoro-2,3-dichloropropane (243db).
 34. The composition ofclaim 33, wherein the composition comprises3-chloro-1,1,1-trifluoropropane (253fb), 3,3,3-trifluoroprop-1-ene(1243zf), and 2-chloro-3,3,3-trifluoropropene (1233xf).
 35. Thecomposition of claim 34, wherein the composition comprises: about 95 toabout 99 percent 3,3,3-trifluoroprop-1-ene (1243zf); about 1 to about 2percent 3-chloro-1,1,1-trifluoropropane (253fb); and about 0.1 to about0.2 percent 2-chloro-3,3,3-trifluoropropene (1233xf), as measured byGC-MS; or about 98 to about 99 percent 3,3,3-trifluoroprop-1-ene(1243zf); about 1 to about 2 percent 3-chloro-1,1,1-trifluoropropane(253fb); and about 0.1 to about 0.2 percent2-chloro-3,3,3-trifluoropropene (1233xf), as measured by GC-MS. 36.(canceled)
 37. The composition of claim 33, wherein the compositioncomprises 3-chloro-1,1,1-trifluoropropane (253fb),3,3,3-trifluoroprop-1-ene (1243zf), 1,1,1,3-tetrafluoropropane (254fb),and 2-chloro-3,3,3-trifluoropropene (1233xf).
 38. The composition ofclaim 37, wherein the composition comprises: about 70 to about 80percent 3,3,3-trifluoroprop-1-ene (1243zf); about 20 to about 25 percent3-chloro-1,1,1-trifluoropropane (253fb); about 0.05 to about 0.1 percent2-chloro-3,3,3-trifluoropropene (1233xf); and about 0.01 to about 0.05percent 1,1,1,3-tetrafluoropropane (254fb), as measured by GC-MS; orabout 74 to about 76 percent 3,3,3-trifluoroprop-1-ene (1243zf); about23 to about 25 percent 3-chloro-1,1,1-trifluoropropane (253fb); about0.05 to about 0.07 percent 2-chloro-3,3,3-trifluoropropene (1233xf); andabout 0.01 to 0.02 percent 1,1,1,3-tetrafluoropropane (254fb), asmeasured by GC-MS.
 39. (canceled)
 40. The composition of claim 33,wherein the composition comprises 3-chloro-1,1,1-trifluoropropane(253fb), 3,3,3-trifluoroprop-1-ene (1243zf),1,1,1-trifluoro-2,3-dichloropropane (243db), and2-chloro-3,3,3-trifluoropropene (1233xf).
 41. The composition of claim33, wherein the composition comprises 3-chloro-1,1,1-trifluoropropane(253fb), 1,1,1-trifluoro-2,3-dichloropropane (243db).
 42. Thecomposition of claim 41, wherein the composition further comprises acatalyst.
 43. The composition of claim 33, wherein the composition issubstantially free of a catalyst.